JP2023505535A - Chemical and physical sunscreen dry compositions, emulsions and/or fluids and their use - Google Patents

Abstract

The present invention relates to a dry chemical and physical sunscreen composition comprising (a) at least one calcium carbonate and (b) the dry weight of the at least one calcium carbonate of (a) 0.1% to 100% by weight of at least one lignin based on the Furthermore, the present invention relates to fluid compositions containing the dry composition according to the invention and emulsions containing the dry composition according to the invention. The invention also relates to the use of the compositions according to the invention for sun protection of plants and plant parts, and the use of emulsions according to the invention for chemical and physical sun protection in cosmetic formulations.

Description

The present invention relates to a dry chemical and physical sunscreen composition comprising (a) at least one calcium carbonate, and (b) the dry weight of the at least one calcium carbonate of (a) 0.1% to 100% by weight of at least one lignin based on the Furthermore, the present invention relates to fluid compositions containing the dry composition according to the invention and emulsions containing the dry composition according to the invention. The invention also relates to the use of the compositions according to the invention for sun protection of plants and plant parts, and the use of emulsions according to the invention for chemical and physical sun protection in cosmetic formulations.

It is widely known that solar energy, and the predominantly ultraviolet part of the solar spectrum, has a damaging effect on living cells, especially on plants and plant parts, but also on human skin. In particular, ultraviolet B (UV-B) radiation in the range of 280-320 nm and ultraviolet A (UV-A) radiation in the range of >320-400 nm both cause sunburn in plants and plant parts. Especially when the air temperature in the shade exceeds a temperature of about 30° C., plants and plant parts and especially fruits can be damaged by sunburn. Such "fruit sunburn" results in fruit damage and a reduction in overall production yield, with economic consequences mainly during the hot summer months.

In addition, ultraviolet A (UV-A) and ultraviolet B (UV-B) radiation damage human DNA through the formation of free radicals and other reactive species that occur via phototoxic reactions in the epidermis and dermis of the skin. . As a result, UV-B and UV-A radiation is considered a major factor in promoting chronic photo-induced changes such as premature aging of the skin and the development of skin cancer.

Therefore, it is becoming increasingly important to protect living cells from sunburn. In particular, it is becoming increasingly important to protect at least some of the plants and parts of plants, especially fruits exposed to sunlight, against UV-B and UV-A radiation. There is also a need to protect sun-exposed human skin from UV-B and UV-A radiation. Several attempts have been made in the art to provide such UV protection.

One attempt to protect plants from sunburn is by obscuring living cells from sunlight with an opaque material such as foil or fabric. For example, China Utility Model Registration No. 203538002 refers to a pomegranate cultivation bag that can prevent sunburn, one side of the pomegranate cultivation bag is reflective and the other side is transparent. be. During hot seasons, this pomegranate growing bag has the sun-facing reflective side covering the top of the pomegranate to reflect most of the daytime sunlight to prevent the pomegranate from sunburning, and is reflected by the reflective plastic film. Some of the sunlight hits the shaded leaves of the fruit trees and increases photosynthesis throughout the orchard. However, such procedures are complicated, time consuming and labor intensive as every plant or fruit must be individually treated by hand.

Another option for reducing the possibility of sunburn is to use mineral particles, usually clay or calcium carbonate, which form a thin film on plants and plant parts or on human skin. and protect living cells by reflecting or absorbing damaging UV radiation. These compounds are therefore known as physical sunscreen agents. Such sunscreen compositions for botanical application are known, for example US Patent Application Publication No. 2012/0052187 A1, which describes titanium dioxide (TiO ₂ ), zinc oxide (ZnO), silicon dioxide ( _SiO2 ), a surfactant, a wetting agent, a dispersant (SWD), and water. This composition forms a suspension concentrate which, when diluted in water, provides a solution that gives uniform coverage using conventional spray equipment.

WO2010/008476 A1 discloses a method for improving crop yield comprising controlling plant tissue stress by at least partially coating the plant tissue with a composition comprising an agricultural sunscreen formulation and a second pesticide. It relates to a method for increasing. The agricultural sunscreen formulation may contain 40-80% by weight calcium carbonate, 1-5% by weight bicarbonate, and 15-59% by weight water.

US Patent Application Publication No. 2016/037772 A1 relates to methods of treating plants to increase tolerance to abiotic stress in plants or to reduce the consequences of abiotic stress in plants. Kaolin or calcium carbonate or the like can be added to the sunscreen.

US Patent Application Publication No. 2017/333301 A1 discloses an oil containing 6-40% by weight of a UV protectant; an organically modified clay mineral; an oil phase thickener; It relates to medium-water type emulsion sunscreen cosmetics. The UV protectant can be particles of metal oxides such as zinc oxide, titanium oxide, iron oxide, cerium oxide, and tungsten oxide.

Inorganic UV filters such as zinc oxide and titanium dioxide are photostable and provide broad spectrum protection covering UV-A and UV-B by blocking UV light. So-called only mineral (inorganic) sunscreen formulations, i.e. sunscreen formulations containing only inorganic UV filter materials such as zinc oxide and/or titanium dioxide, have long been used in particular for infants and young children as well as for people with sensitive skin. has also been recommended. However, inorganic UV filters are mainly used in the form of nanoparticles and it has recently been believed that these nanoparticles can have a detrimental effect on nature and human skin.

The article " _TiO2 Encapsulated in Lignin-Based Colloidal Spheres for High Sunscreen Performance and Weak Photocatalytic Activity", Yuan Yuan Li et al. , ACS Sustainable Chemistry and Engineering, vol. 7, no. 6, Feb. 18, 2019, relates to well-entrapped nano- _TiO2 particles in lignin colloid spheres. However, as already mentioned above, TiO ₂ nanoparticles can have a detrimental effect on natural and human skin. Furthermore, colloidal spheres exhibit different chemical performance than, for example, particles coated with lignin on the particles.

The article "Lignin Coating Quenching the Photocatalytic Activity of Titanium Dioxide Nanoparticles for Potential Skin Care Applications", M. et al. Morsella et al. , RSC Advances, vol. 5, no. 71, Jan. 1, 2015, relates to coatings to suppress the photocatalytic activity of titanium dioxide nanoparticles for potential skin care applications. However, as already mentioned above, TiO ₂ nanoparticles can have a detrimental effect on natural and human skin. Furthermore, this document relates to photocatalytic activity different from UV activity.

Another option to reduce the possibility of sunburn is to use organic UV filters. Organic UV filters are often transparent or translucent. Such filters provide chemical sun protection by absorbing UV-A and/or UV-B radiation. Organic UV filters can be divided into synthetically produced UV filters and naturally occurring UV filters. Synthetically produced UV filters are not naturally occurring and are produced synthetically, whereas naturally occurring UV filters are naturally occurring or produced from naturally occurring compounds.

For example, synthetically produced UV filters such as octocrylene can be designed to be perfectly compatible with the respective system or composition with which they are blended. Moreover, such filters can be customized for individual applications. However, synthetic organic UV filters, such as for example octocrylene, are suspected of being a possible cause of dermatitis and skin allergies, especially in persons with sensitive skin, and of their potentially harmful effects on the environment, and thus an ever-increasing concern. exposed to

Accordingly, the art is aware of suitable formulations providing adequate or improved UV-B and/or UV-A protection for living cells, in particular for plants and plant parts and human skin. or there is a continuing need for the composition.

It is therefore an object of the present invention to provide compositions for providing chemical and physical sun protection. More precisely, the object of the present invention is a composition for providing sufficient or improved UV-B and/or UV-A protection to living cells, in particular plants and plant parts and human skin, By different mechanisms, namely by reflecting UV-B and/or UV-A radiation and by absorbing UV-B and/or UV-A radiation. It is a further object of the present invention that the compounds used in these compositions are non-toxic to humans, do not have a detrimental effect on the environment, and preferably to plants and plant parts, especially fruits. Approved by the food regulations used and by the FDA for use in cosmetic applications. Another object of the invention is that the composition should be easy and fast to produce, inexpensive and above all easy to handle. It is particularly preferred that these compositions adhere to plants and plant parts and human skin and are not easily washed off by rain or perspiration.

These and other objects of the present invention can be met by the chemical and physical sunscreen composition as described herein and defined in the claims. Advantageous embodiments of the invention are defined in the corresponding dependent claims.

According to one embodiment of the present invention, there is provided a dry chemical and physical sunscreen composition comprising (a) at least one calcium carbonate, and (b) at least one of (a) 0.1% to 100% by weight of at least one lignin, based on the dry weight of calcium carbonate.

The inventors have surprisingly found that the compositions described above provide sufficient or improved chemical and physical sun protection. More precisely, the inventors have surprisingly found that the compositions of the invention are able to react by different mechanisms, namely by reflecting UV-B and/or UV-A radiation and by UV-B and/or UV-A radiation. It has been found that by absorbing UV-A radiation, it provides two different mechanisms for UV-B and/or UV-A protection for living cells, especially plants and plant parts, and human skin. rice field. The combination of at least one calcium carbonate and at least one lignin provides new and improved UV protection mechanisms not achievable with bare minerals, especially bare calcium carbonate. Furthermore, the compounds used in the compositions of the present invention, namely calcium carbonate and lignin, are non-toxic to humans and do not have a detrimental effect on the environment. These compounds are also often approved by food legislation for use on plants and plant parts, especially fruits, and by the FDA for use in cosmetic applications. Furthermore, the inventors have surprisingly found that the compositions of the invention can be produced easily and quickly, are inexpensive and, above all, easy to handle. Furthermore, when the composition according to the invention is used for sun protection of plants and plant parts, another advantage is that the composition provides the plant with calcium nutrients due to the calcium carbonate in the composition. to provide more.

According to another aspect of the present invention there is provided a chemical and physical sunscreen fluid composition comprising water and 1 to 100% by weight, based on the weight of water, of a dry composition according to the invention. Including things. Yet another advantage is that when the fluid composition is used on plants and plant parts, the layer of composition formed on the plants and plant parts also repels insects.

According to another aspect of the present invention there is provided a chemical and physical sunscreen emulsion, the emulsion comprising a water-in-oil or oil-in-water mixture, comprising a water-in-oil or oil-in-water mixture from 0.1 to 100% by weight of the dry composition according to the present invention.

According to another aspect of the invention, the compositions according to the invention are used for sun protection of plants and plant parts, wherein this sun protection includes physical and chemical protection.

According to another aspect of the invention, the emulsions of the invention are used for chemical and physical sun protection in cosmetic formulations.

Advantageous embodiments of the above aspects are defined in the corresponding dependent claims.

According to one embodiment of the invention, the calcium carbonate is ground calcium carbonate (GCC), preferably marble, limestone and/or chalk; precipitated calcium carbonate (PCC), preferably vaterite, calcite and/or or aragonite; and mixtures thereof, most preferably the calcium carbonate is ground calcium carbonate.

According to another embodiment of the invention, the at least one calcium carbonate is
(a) a weight median particle size _d50 value in the range 0.05 μm to 20 μm, preferably 0.25 μm to 10 μm, most preferably 0.5 μm to 8 μm, and/or (b) ≦100 μm, preferably ≦60 μm, more preferably ≦45 μm, most preferably ≦20 μm topcut (d ₉₈ ), and/or (c) 0.5-100 m ² /g, preferably 0.5-50 m ^{2 /g} , measured by the BET nitrogen method g, more preferably 0.5-35 m ² /g, most preferably 0.5-10 m ² /g.

According to another embodiment of the invention, the at least one lignin is natural lignin, Clarson lignin, hydrolyzed lignin, ground lignin (crushed wood lignin), soda lignin, organosolv lignin, kraft lignin, sulfonated lignin and mixtures thereof, preferably water-insoluble lignins selected from the group consisting of Clarson lignin, kraft lignin, and mixtures thereof, most preferably is kraft lignin.

According to another embodiment of the present invention, the at least one lignin is in an amount of 1-50% by weight, preferably in an amount of 3-30% by weight, based on the dry weight of the at least one calcium carbonate of (a) and most preferably present in the composition in an amount of 5-25% by weight.

According to another embodiment of the present invention, the composition further comprises an organic solvent, preferably in an amount of 5-50% by weight, based on the dry weight of the at least one calcium carbonate of (a), more preferably in an amount of 10-40% by weight, most preferably in an amount of 15-35% by weight and/or preferably in an amount of 100-500% by weight, based on the dry weight of the at least one lignin of (b) and more preferably in an amount of 150-450% by weight and most preferably in an amount of 200-300% by weight of the organic solvent.

According to another embodiment of the invention, the organic solvent is hexane, toluene, methanol, ethanol, dioxane, acetone, dimethylsulfoxide, dimethylformamide, ethylene glycol, ethyl acetate, glycerol, γ-valerolactone, polyethylene glycol, polypropylene. glycols, and mixtures thereof, more preferably selected from the group consisting of ethylene glycol, ethyl acetate, glycerol, γ-valerolactone, polyethylene glycol, polypropylene glycol, and mixtures thereof, most preferably γ-valerolactone.

According to another embodiment of the invention, the at least one lignin is present in the composition in the form of a mixture with the at least one calcium carbonate or in the form of a coating on the at least one calcium carbonate, preferably , is present as a coating on at least one calcium carbonate.

According to another embodiment of the invention, the at least one lignin in the coating on the at least one calcium carbonate is a water-insoluble lignin, preferably kraft lignin.

According to another embodiment of the present invention the fluid composition further comprises a surfactant, preferably acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, isocrotonic acid, aconitic acid (cis or trans), mesaconic acid, sinapinic acid, undecylenic acid, angelic acid, canellic acid, hydroxyacrylic acid, acrolein, acrylamide, acrylonitrile, dimethylaminoethyl methacrylate, vinylpyrrolidone, vinylcaprolactam, ethylene, propylene, Isobutylene, diisobutylene, vinyl acetate, styrene, α-methylstyrene, methyl vinyl ketone, esters of acrylic and methacrylic acid, organomodified trisiloxanes, PEG, polyglycerol-esters, sophorolipids, polyether monomers and/or comonomers. and mixtures thereof, most preferably poly(acrylic acid) and/or poly(methacrylic acid), and/or said surfactant comprises (a) most preferably in an amount of 0.0001 to 0.2% by weight, preferably in an amount of 0.001 to 0.1% by weight, based on the dry weight of the at least one calcium carbonate and the at least one lignin of (b) is present in the composition in an amount of 0.005-0.05% by weight.

According to another embodiment of the invention, the plants and plant parts are fruits, vegetables, trees, seeds, leaves, wood, nuts, agricultural crops, crop plants and flowers.

According to another embodiment of the invention, the at least one lignin is present in the form of a coating on the at least one calcium carbonate and/or the at least one lignin is water-insoluble lignin, preferably kraft lignin. .

According to another embodiment of the invention, the cosmetic formulation is a sunscreen product, a facial makeup product, a hair care product, a hair styling product, a nail care product, a hand care product, a skin care product, and mixtures thereof.

For purposes of the present invention, the following terms shall be understood to have the following meanings:

"Chemical sun protection" in the sense of the present invention refers to UV-B and/or UV-A radiation protection by absorbing UV-B and/or UV-A radiation.

"Physical sun protection" in the sense of the present invention refers to UV-B and/or UV-A radiation protection by reflecting UV-B and/or UV-A radiation.

"UV-A protection" and "UV-B protection" in the sense of the present invention refer to ultraviolet B (UV-B) radiation in the range 280-320 nm and ultraviolet A (UV-A) radiation in the range >320-400 nm. ) radiation, both of which refer to protection from radiation that causes sunburn in plants and plant parts and in human skin.

A "water-insoluble" material is defined as a mixture of 100 g of the material with 100 g of deionized water, at 20° C. under atmospheric pressure, and filtration over a 0.2 μm pore size filter to recover the liquid filtrate. It is defined as a material that gives 0.1 g or less of recovered solid material after evaporation of 100 g of this liquid filtrate at 95-100° C. under pressure. Thus, a "water-soluble" material is defined as when 100 g of the material is mixed with 100 g of deionized water and filtered on a 0.2 μm pore size filter at atmospheric pressure at 20° C. and the liquid filtrate is recovered. , is defined as a material that gives 0.1 g or more of recovered solid material after evaporation of 100 g of this liquid filtrate at 95-100° C. under ambient pressure.

The "particle size" of the particulate material herein is described by the distribution of particle sizes _dx . Here the value _dx represents the diameter for which x weight percent of the particles have a diameter smaller than _dx . This means, for example, that the _d20 value is that 20% by weight of all particles are smaller than the particle size. The _d50 value is therefore the weight median particle size, ie 50% by weight of all particles are larger than this particle size and the remaining 50% by weight are smaller than this particle size. For the purposes of the present invention, particle size is specified as weight median particle size d ₅₀ unless otherwise stated. d ₉₈ is the particle size below which 98% by weight of all particles are smaller. The _d98 value is also specified as "top cut". Particle size was determined using a Sedigraph® 5100 instrument from Micromeritics Instrument Corporation. This method and instrumentation are known to those skilled in the art and are commonly used to determine the particle size of fillers and pigments. Measurements were carried out in an aqueous solution of 0.1% by weight Na ₄ P ₂ O ₇ . A high speed stirrer and sonication were used to disperse the sample.

The "specific surface area (SSA)" of a calcium carbonate-containing filler material in the sense of the present invention is defined as the surface area of the calcium carbonate-containing filler material divided by its mass. The specific surface area referred to here is measured by a nitrogen gas adsorption method using a BET isotherm (ISO 9277:2010) and is defined in m ² /g.

The term "dry" material or "dry" composition is understood to be a material/composition having less than 5.0% water by weight relative to the weight of the material/composition. The % of water (equivalent to total residual water content) was determined according to the coulometric Karl Fischer method, where the material/composition was heated to 220° C., released as vapor, and nitrogen gas flow (100 ml/min ) is measured with a coulometric Karl Fischer apparatus.

"Coating" in the sense of the invention means that one compound is located on the surface of another compound.

Where the term "comprising" or "containing" is used in the specification and claims, it does not exclude other elements. For the purposes of the present invention, the term "consisting of" is considered to be a preferred embodiment of the term "comprising." In the following, where a group is defined to include at least a certain number of embodiments, it should be understood that this preferably also discloses the group consisting only of those embodiments. .

Where an indefinite or definite article is used when referring to a singular noun, for example "a", "an" or "the", this includes the plural of that noun unless otherwise specified.

Terms such as “obtainable” or “defined” and “obtained” or “defined” are used interchangeably used for For example, this means that, unless the context clearly dictates otherwise, the term "obtained" may, for example, indicate that an embodiment may, for example, follow the order of steps following the term "obtained." Although it is not meant to indicate that it must be obtained by It means included.

Details and preferred embodiments of the present invention are described in more detail below. Embodiments referring to the compositions and emulsions of the invention also refer to the use of the compositions of the invention for sun protection of plants and plant parts, and the emulsions of the invention for chemical and physical sun protection in cosmetic formulations. and refers to the use of the compositions according to the invention for sun protection of plants and plant parts, and the use of the emulsions according to the invention for chemical and physical sun protection in cosmetic formulations. The embodiments also relate to embodiments of the compositions and emulsions of the present invention.

According to the present invention there is provided a dry dry composition for chemical and physical sun protection, comprising (a) at least one calcium carbonate, and (b) at least one calcium carbonate of (a) 0.1% to 100% by weight of at least one lignin based on the dry weight of the

At least one calcium carbonate According to the present invention, at least one calcium carbonate is present in the dry composition.

The term "at least one" calcium carbonate in the sense of the invention means that the calcium carbonate comprises one or more calcium carbonates and preferably consists of one or more calcium carbonates.

In one embodiment of the invention, the at least one calcium carbonate in the composition preferably comprises and preferably consists of one calcium carbonate. Alternatively, the at least one calcium carbonate comprises two or more calcium carbonates, preferably consisting of two or more calcium carbonates. For example, the at least one calcium carbonate comprises two or three calcium carbonates, preferably two or three calcium carbonates.

The amount of calcium in the calcium carbonate is at least 50 mol %, preferably at least 70 mol %, more preferably at least 90 mol % and most preferably at least 99 mol %, relative to the total amount of calcium carbonate. Calcium carbonate can contain additional alkaline earth compounds such as Mg.

According to a preferred embodiment of the invention, the calcium carbonate is ground calcium carbonate (GCC), preferably marble, limestone and/or chalk; precipitated calcium carbonate (PCC), preferably vaterite, calcite and/or aragonite; and mixtures thereof.

Natural or ground calcium carbonate (GCC) is understood to be produced from naturally occurring forms of calcium carbonate mined from sedimentary rocks such as limestone or chalk, or from metamorphic marble rocks, eggshells, or shells. Calcium carbonate is known to exist as three types of crystal polymorphs: calcite, aragonite, and vaterite. Calcite, the most common crystalline polymorph, is believed to be the most stable crystalline form of calcium carbonate. Less common is aragonite, which has a discrete or clustered acicular orthorhombic crystal structure. Vaterite is the rarest calcium carbonate polymorph and is generally unstable. Ground calcium carbonate is almost exclusively the calcite polymorph, which is said to be trigonal-rhombohedral and represents the most stable form of calcium carbonate polymorph. The term "source" for calcium carbonate in the meaning of this application refers to the naturally occurring mineral material from which calcium carbonate is obtained. The source of calcium carbonate may further comprise naturally occurring components such as aluminosilicates and the like.

Generally, comminution of natural ground calcium carbonate may be a dry or wet comminution process, e.g., using any conventional comminution equipment under conditions such that comminution occurs primarily as a result of impact by secondary objects. ball mill, rod mill, vibrating mill, roll crusher, centrifugal impact mill, vertical bead mill, attrition mill, pin mill, hammer mill, grinder, shredder, declamper, knife cutter, or any other known to those skilled in the art. It can be implemented in one or more of other such devices. When the mineral material comprising calcium carbonate comprises a mineral material comprising wet ground calcium carbonate, the grinding step may be performed under conditions such that autogenous grinding occurs and/or horizontal ball milling and/or other methods known to those skilled in the art. can be done by such a process. The wet-processed ground calcium carbonate-containing mineral material thus obtained can be washed and dewatered by well-known processes, such as flocculation, filtration, or forced evaporation, before drying. A subsequent drying step (if desired) can be carried out in a single step, such as spray drying, or can be carried out in at least two steps. Such mineral materials are also commonly subjected to beneficiation processes (eg, flotation, bleaching, or magnetic separation processes, etc.) to remove impurities.

According to one embodiment of the invention, the source of natural or ground calcium carbonate (GCC) is selected from marble, chalk, limestone, or mixtures thereof. Preferably, the source of ground calcium carbonate is marble. According to one embodiment of the invention, the GCC is obtained by dry grinding. According to another embodiment of the invention, the GCC is obtained by wet grinding and optionally subsequent drying.

According to one embodiment of the invention, the calcium carbonate comprises one type of ground calcium carbonate. According to another embodiment of the invention, the calcium carbonate comprises a mixture of two or more types of ground calcium carbonate selected from different sources.

"Precipitated calcium carbonate" (PCC) in the sense of the present invention generally means either by precipitation following the reaction of carbon dioxide with lime in an aqueous environment, or by precipitation of calcium and carbonate ion sources in water, or by precipitation of calcium It is a synthesized substance obtained by precipitation from solution with a combination of ions and carbonate ions, for example CaCl ₂ and Na ₂ CO ₃ . A further possible method of producing PCC is the lime-soda process, or the Solvay process, in which PCC is a by-product of ammonia production. Precipitated calcium carbonate exists in three primary crystalline forms, calcite, aragonite, and vaterite, and many different polymorphs (crystal habits) exist for each of these crystalline forms. Calcite has typical scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonal prismatic, tectonic, colloidal (C-PCC), cubic, prismatic (P-PCC), etc. It has a trigonal crystal structure with a certain crystal habit. Aragonite has an orthorhombic structure with typical crystal habits of twinned hexagonal prisms, as well as thin elongated prisms, curved blades, steep cones, chiselled crystals, branched tree morphologies, and coralline morphologies. or have structures with various assortments of worm-like morphologies. Vaterite belongs to the hexagonal crystal system. The resulting PCC slurry can be mechanically dewatered and dried.

According to one embodiment of the invention, the precipitated calcium carbonate is precipitated calcium carbonate, preferably comprising the mineralogical crystal forms of aragonite, vaterite, or calcite, or mixtures thereof.

According to one embodiment of the invention, the calcium carbonate comprises one type of precipitated calcium carbonate. According to another embodiment of the invention, the calcium carbonate comprises a mixture of two or more precipitated calcium carbonates selected from different crystalline forms and different polymorphs of precipitated calcium carbonate. For example, the at least one precipitated calcium carbonate can include one PCC selected from S-PCC and one PCC selected from R-PCC.

According to a preferred embodiment of the invention, the at least one calcium carbonate-containing material is ground calcium carbonate, preferably dry ground calcium carbonate. According to another preferred embodiment, the at least one calcium carbonate-containing material is marble.

Preferably, the at least one calcium carbonate is a dry-ground material, a wet-ground and dry material, or a mixture of the aforementioned materials. Generally, the comminution step can be carried out using any conventional comminution equipment, i.e. ball mills, rod mills, vibratory mills, e.g. under conditions such that purification occurs primarily as a result of impact by secondary objects. , roll crusher, centrifugal impact mill, vertical bead mill, attrition mill, pin mill, hammer mill, crusher, shredder, declamper, knife cutter, or other such equipment known to those skilled in the art. can be implemented.

When the at least one calcium carbonate is wet ground calcium carbonate, the grinding step may be performed under conditions such that autogenous grinding occurs, and/or horizontal ball milling, and/or other such processes known to those skilled in the art. It can be done by process. The wet-processed ground calcium carbonate thus obtained can be washed and dewatered by well-known processes, such as flocculation, filtration, or forced evaporation, before drying. Subsequent drying steps can be carried out in a single step, such as spray drying, or in at least two steps, e.g., applying a first heating step to the calcium carbonate, thereby reducing the associated moisture content to to a level of no more than about 5% by weight relative to the total dry weight of the . The total residual moisture content of the filler was determined by desorbing moisture in an oven at 195° C. and using dry _N2 at 100 ml/min for 10 minutes with a KF coulometer (Mettler Toledo coulometric KF titration combined with a Mettler oven DO 0337). It can be measured by Karl Fischer coulometric titration by continuous passage through apparatus C30). The total residual moisture content can be determined using a calibration curve and can be considered blind in gas flow for 10 minutes without sample. The residual total moisture content can be further reduced by applying a second heating step to the calcium carbonate. If this drying is carried out by more than one drying step, the first step can be carried out by heating in a stream of hot air, while the second and further drying steps are preferably carried out by corresponding It is carried out by indirect heating in which the atmosphere in the container contains a surface treatment agent. Calcium carbonate is also commonly subjected to beneficiation processes (such as flotation, bleaching, or magnetic separation processes) to remove impurities.

In one embodiment of the invention, the at least one calcium carbonate comprises dry ground calcium carbonate. In another preferred embodiment, the at least one calcium carbonate is a raw material that is wet milled in a horizontal ball mill and subsequently dried by using the well known process of spray drying.

Depending on the at least one calcium carbonate, the at least one calcium carbonate according to the invention is less than 5% by weight, preferably less than 4% by weight, more preferably less than 3% by weight, based on the total dry weight of the at least one calcium carbonate. , even more preferably less than 2% by weight, most preferably less than 1% by weight.

Alternatively, the at least one calcium carbonate according to one embodiment comprises 0.01 to 1 wt%, preferably 0.02 to 0.5 wt%, more preferably 0.02 to 0.5 wt%, based on the total dry weight of the at least one calcium carbonate. It may have a residual total moisture content of 03-0.3 wt%, even more preferably 0.04-0.2 wt%, and most preferably 0.05-0.15 wt%.

For example, when wet-milled and dried calcium carbonate is used as the at least one calcium carbonate, the residual total moisture content of the at least one calcium carbonate is preferably 0, based on the total dry weight of the at least one calcium carbonate. 0.01 to 1 wt%, more preferably 0.02 to 0.1 wt%, most preferably 0.04 to 0.08 wt%. When using PCC as the at least one calcium carbonate, the residual total water content of the at least one calcium carbonate is preferably 0.01 to 1% by weight, more preferably 0.01 to 1% by weight, based on the total dry weight of the at least one calcium carbonate. is 0.05-0.2% by weight, most preferably 0.05-0.15% by weight.

According to one embodiment of the invention, the at least one calcium carbonate is preferably in the form of a particulate material, such as is conventionally used for the material or materials involved in the type of product being manufactured. It can have a particle size distribution. Generally, the at least one calcium carbonate preferably has a weight median particle size d ₅₀ in the range 0.05 μm to 20 μm, preferably 0.25 μm to 10 μm, most preferably 0.5 μm to 8 μm.

Additionally or alternatively, at least one calcium carbonate has a top cut ( _d98 ) of ≤100 μm, preferably ≤60 μm, more preferably ≤45 μm, most preferably ≤20 μm.

Additionally or alternatively, the at least one calcium carbonate has an amount of 0.5 to 100 m ² /g, preferably 0.5 to 50 m ² /g, more preferably 0.5 to 35 m ^{2 /} g, measured by the BET nitrogen method. g, most preferably from 0.5 to 10 m ² /g.

According to another embodiment of the invention, the at least one calcium carbonate has:
(a) a weight median particle size _d50 value in the range 0.05 μm to 20 μm, preferably 0.25 μm to 10 μm, most preferably 0.5 μm to 8 μm, or (b) ≦100 μm, preferably ≦60 μm, more preferably or (c) 0.5 to 100 m 2 /g _, preferably 0.5 to 50 m ² /g, more preferably 0.5 to 50 m ² /g, measured by the BET nitrogen method. specific surface area (BET) of 0.5 to 35 m ² /g, most preferably 0.5 to 10 m ² /g.

According to another embodiment of the invention, the at least one calcium carbonate has:
(a) a weight median particle size _d50 value in the range 0.05 μm to 20 μm, preferably 0.25 μm to 10 μm, most preferably 0.5 μm to 8 μm, and (b) ≦100 μm, preferably ≦60 μm, more preferably is ≦45 μm, most preferably ≦20 μm, and (c) 0.5-100 m ² /g, preferably 0.5-50 m 2 /g, more preferably 0.5-50 m ² /g, measured by _the BET nitrogen method. specific surface area (BET) of 0.5 to 35 m ² /g, most preferably 0.5 to 10 m ² /g.

At least one lignin According to the present invention, at least one lignin is present in the composition in an amount of 0.1% to 100% by weight, based on the dry weight of the at least one calcium carbonate.

The term "at least one" lignin in the sense of the invention means that the lignin comprises one or more lignins, preferably consists of one or more lignins.

In one embodiment of the invention, the at least one lignin in the composition comprises, preferably consists of, one lignin. Alternatively, the at least one lignin comprises two or more lignins, preferably consists of two or more lignins. For example, the at least one lignin comprises two or three lignins, preferably two or three lignins.

Preferably, the at least one lignin in the composition comprises one lignin, more preferably consists of one lignin.

"Lignin" in the sense of the present invention is defined as an organic biopolymer obtained from wood and plants. Lignin is a crosslinked polymer with a molecular weight greater than 10000 u. Lignin is rich in hydrophobic and aromatic subunits and contains mainly crosslinked networks of 4-hydroxy-3-methoxyphenylpropane, 3,5-dimethoxy-4-hydroxyphenylpropane, and 4-hydroxyphenylpropane.

Lignin is known to those skilled in the art and commercially available, for example, from Domshow under the trade name Domshow Lignin DS10.

Plant lignins can be broadly divided into three classes: coniferous (gymnosperm) lignins, broadleaf (angiosperm) lignins, and grass or annual (grass) lignins. Three different phenylpropane units, these monolignols, are responsible for lignin biosynthesis. Guiacyl lignins are composed primarily of coniferyl alcohol units, whereas guaiacyl-syringyl lignins contain monomeric units of coniferyl alcohol and sinapyl alcohol. In general, guaiacyl lignin is present in softwoods and guaiacyl-syringyl lignin is present in hardwoods. Gramineous lignin is mainly composed of p-coumaryl alcohol units. Lignin polymerization is initiated by oxidation of the phenolic hydroxyl groups of phenylpropane. Radical stabilization occurs by coupling to another radical at any position of the unpaired electron.

According to one embodiment of the invention, the at least one lignin is from natural lignin, Clason lignin, hydrolyzed lignin, ground lignin, soda lignin, organosolv lignin, kraft lignin, sulfonated lignin, and mixtures thereof. A water-soluble or water-insoluble lignin selected from the group consisting of

Native lignin is lignin present in plant tissues, also known as native lignin.

Clarson lignin is an acid-insoluble lignin inclusion in natural lignin. Clason lignin is obtained by prehydrolyzing native lignin in _H2SO4 , hydrolyzing the mixture at _elevated temperature and filtering. The residue contains Klason lignin. This Klason process is known to those skilled in the art.

Hydrolyzed lignin is obtained by refluxing lignin or lignocellulose with HCl in a dioxane/water composition. This treatment results in the degradation of lignin with the formation of substantial amounts of allylpropane, the majority of the acid-decomposed monomers being derived from the allylglycerol β-aryl ether structure.

Ground lignin (or milled wood lignin; MWL), also known as Bjorkmann lignin, is produced by grinding wood flour in a ball mill either in the dry state or in the presence of a non-swelling solvent such as toluene. where the cellular structure of the wood is destroyed. A portion of the lignin can be obtained from the suspension by extraction with a dioxane-water mixture. The Bjoerkman process is known to those skilled in the art.

Kraft lignin is lignin obtained from kraft processing, also known as kraft pulping or sulfate processing. This process is known to those skilled in the art for converting wood into wood pulp, which consists of nearly pure cellulosic fibers, the main component of paper. The kraft process involves treating wood chips with a hot mixture of water, sodium hydroxide (NaOH), and sodium sulfide ( _Na2S ), known as white liquor, to convert lignin, hemicellulose, and cellulose. Breaks the linking bond. This technique involves several steps, both mechanical and chemical.

Lignosulfonates, also known as sulfonated lignins, are water-soluble anionic polyelectrolyte polymers. They are obtained from wood by treating the wood with a solution containing sulfur dioxide and bisulfite ions at elevated temperatures. This process is also known to those skilled in the art.

Soda lignin is obtained from the soda process, which involves heating fibrous wood material in a pressure reactor to high temperatures in the presence of sodium hydroxide (ie, soda), also known as cooking liquor. In this process, lignin is separated from cellulose and suspended in a liquid phase called black liquor. Black liquor thus contains lignin and sodium hydroxide (soda) and is known as soda lignin.

Organosolv lignin is obtained by the organosolv method. Organosolv processes typically involve the extraction of lignin from lignocellulosic biomass using organic solvents with acidic catalysts. Organosolv lignins do not contain sulfur or sulfonate groups and have a molecular weight of about 1000-2000 g/mol.

According to one embodiment of the invention, the at least one lignin is a mixture of two or more lignins, such as a mixture of two lignins, such as a sulfonated lignin, and a further lignin, such as a sulfonated lignin and kraft lignin or natural lignin.

According to a preferred embodiment of the invention, the at least one lignin consists of only one lignin, preferably native lignin, Clarson lignin, hydrolyzed lignin, ground lignin, soda lignin, organosolv lignin, kraft lignin. or sulfonated lignin, most preferably consisting only of kraft lignin.

According to one embodiment of the invention the at least one lignin is a water soluble lignin. According to another embodiment of the invention the at least one lignin is a water insoluble lignin. Preferably, the at least one lignin is a water-insoluble lignin, most preferably the at least one water-insoluble lignin is selected from the group consisting of Clason lignin, kraft lignin, and mixtures thereof, most preferably kraft lignin. is.

According to another embodiment of the invention, the at least one lignin has a molecular weight above 10000 u, preferably between 15000 and 1000000 u, even more preferably between 50000 and 800000 u, most preferably between 100000 and 500000 u. It has a molecular weight of u.

The at least one lignin is present in the composition in an amount of 0.1-100% by weight based on the dry weight of the at least one calcium carbonate in (a). According to a preferred embodiment of the present invention, the at least one lignin is in an amount of 1-50% by weight, preferably 3-30% by weight, based on the dry weight of the at least one calcium carbonate of (a). , most preferably present in the composition in an amount of 5 to 25% by weight.

Dry Composition The dry composition of the present invention for chemical and physical sun protection comprises (a) at least one calcium carbonate, and (b), based on the dry weight of the at least one calcium carbonate of (a), 0.5. 1% to 100% by weight of at least one lignin.

Alternatively, the dry composition of the present invention for chemical and physical sun protection comprises (a) at least one calcium carbonate, and (b) 0.1, based on the dry weight of the at least one calcium carbonate of (a). % to 100% by weight of at least one lignin.

Preferably, the dry composition of the present invention for chemical and physical sun protection comprises (a) at least one calcium carbonate and (b), based on the dry weight of the at least one calcium carbonate of (a), 0.000. 1% to 100% by weight of at least one lignin. In that case, other compounds may be present in the composition.

According to one embodiment of the invention, the composition further comprises an organic solvent.

An "organic solvent" in the sense of the invention is a compound that is liquid at room temperature and is different from water. Room temperature refers to a temperature of 25°C. Preferably, the organic solvent is capable of dissolving at least one lignin, preferably a water-insoluble lignin.

The organic solvent of the invention can be any organic solvent suitable for the compositions of the invention. A person skilled in the art knows how to select such organic solvents. Organic solvents are known to those skilled in the art and are commercially available.

According to one embodiment of the invention, the organic solvent is hexane, toluene, methanol, ethanol, dioxane, acetone, dimethylsulfoxide, dimethylformamide, ethylene glycol, ethyl acetate, glycerol, γ-valerolactone, polyethylene glycol, polypropylene glycol. , and mixtures thereof, more preferably selected from the group consisting of ethylene glycol, ethyl acetate, glycerol, γ-valerolactone, polyethylene glycol, polypropylene glycol, and mixtures thereof, most preferably γ-valerolactone.

Hexane is a alkane of 6 carbon atoms with _the chemical formula: _C6H14 and contains 5 structural isomers. All hexanes are colorless liquids, odorless when pure, with boiling points between 50 and 70°C.

Toluene, an aromatic hydrocarbon with the formula _C6H5CH3 , is _a colorless, water- _insoluble liquid with an odor associated with paint thinners.

Methanol, also known among others as methyl alcohol, is a chemical with the formula: CH ₃ OH. Ethanol, also known inter alia as ethyl alcohol, is a chemical with the formula: CH ₃ —CH ₂ —OH.

Dioxane is a heterocyclic organic compound and is classified as an ether. Dioxane is a colorless liquid with a slightly sweet odor. Dioxane includes isomers of 1,2-dioxane, 1,3-dioxane, and 1,4-dioxane.

Acetone or propanone is an organic compound with the formula: (CH ₃ ) ₂ CO, which is a colorless, volatile, flammable liquid and the simplest and smallest ketone.

Dimethyl sulfoxide (DMSO) is an organosulfur compound having the formula: ( _CH3 ) _2SO . This colorless liquid is a polar aprotic solvent, dissolves both polar and non-polar compounds, and is miscible in a wide range of organic solvents and water.

Dimethylformamide is an organic compound having the formula: ( _CH3 ) _2NC (O)H. This colorless liquid, commonly abbreviated DMF, is miscible with water and most organic liquids.

Ethylene glycol, also known as ethane-1,2-diol, is an organic compound with the chemical formula: (CH ₂ OH) ₂ . Ethylene glycol is an odorless, colorless, sweet-tasting viscous liquid.

Ethyl acetate is an organic compound with the formula: CH ₃ —COO—CH ₂ —CH ₃ . Ethyl acetate is a colorless liquid with a characteristic sweet odor. Ethyl acetate is an ester of ethanol and acetic acid.

Glycerol, also called glycerine or glycerin or propane-1,2,3-triol, is a simple polyol compound. Glycerol is a colorless, odorless, viscous liquid that is sweet-tasting and non-toxic. Glycerol has the chemical formula: CH ₂ OH--CHOH--CH ₂ OH.

γ-Valerolactone is an organic compound having the formula: C ₅ H ₈ O ₂ . This colorless liquid is chiral, but is usually used as a racemate. γ-Valerolactone is readily obtained from cellulosic biomass and is a potential fuel and green solvent.

Polyethylene glycol is a polyether compound that has many uses, from industrial manufacturing to medicine. PEG is also known as polyethylene oxide (PEO) or polyoxyethylene (POE), depending on its molecular weight. The structure of PEG is generally represented by H--(OCH ₂ --CH ₂ ) _n --OH.

Polypropylene glycol or polypropylene oxide is a polymer of propylene glycol. Chemically it is a polyether. The structure of PPG is generally represented by H--(O--CHCH ₃ --CH ₂ ) _n --OH.

According to a preferred embodiment of the invention, the solvent is γ-valerolactone.

According to one embodiment of the present invention, the organic solvent is present in the composition in an amount of 5-50% by weight, more preferably 10-40% by weight, based on the dry weight of the at least one calcium carbonate of (a). It is present in an amount of weight percent, most preferably in an amount of 15-35 weight percent.

Additionally or alternatively, the organic solvent is present in the composition in an amount of 100-500% by weight, more preferably in an amount of 150-450% by weight, based on the dry weight of the at least one lignin of (b). present, most preferably in an amount of 200-300% by weight.

According to one embodiment of the present invention, the organic solvent is in an amount of 5-50% by weight, more preferably in an amount of 10-40% by weight, based on the dry weight of the at least one calcium carbonate of (a), most preferably present in the composition in an amount of 15-35% by weight or present in an amount of 100-500% by weight based on the dry weight of the at least one lignin of (b), more preferably 150 It is present in the composition in an amount of ˜450% by weight, most preferably in an amount of 200-300% by weight.

According to another embodiment of the present invention, the organic solvent is in an amount of 5-50% by weight, more preferably in an amount of 10-40% by weight, based on the dry weight of the at least one calcium carbonate of (a). , most preferably present in the composition in an amount of 15 to 35% by weight and present in an amount of 100 to 500% by weight, more preferably 150 It is present in the composition in an amount of ˜450% by weight, most preferably in an amount of 200-300% by weight.

According to one embodiment of the present invention, the dry composition comprises (a) at least one calcium carbonate and (b) from 0.1% to 100% weight percent of at least one lignin, and (c) an organic solvent

According to another embodiment of the present invention, the dry composition comprises (a) at least one calcium carbonate, and (b) from 0.1% by weight, based on the dry weight of the at least one calcium carbonate of (a), to 100% by weight of at least one lignin and (c) an organic solvent.

The organic solvent may further contain water or may be used in combination with water. However, the amount of water in organic solvents or when used in combination with organic solvents is rather small. More precisely, if water is present in the organic solvent or if water is used in combination with an organic solvent, dry compositions according to the invention are still obtained.

As already mentioned above, a "dry" composition is understood to be a composition having less than 5.0% water, relative to the weight of the composition. Preferably, the dry composition according to the present invention contains less than 4%, more preferably less than 3%, even more preferably less than 2%, most preferably less than 1% by weight, based on the total dry weight of the composition. Contains water.

According to one embodiment of the invention, at least one lignin is present in the composition in the form of a mixture with at least one calcium carbonate. In that case, at least one lignin and at least one calcium carbonate are present in the composition of the invention.

According to another embodiment of the invention, the at least one lignin is present in the composition in the form of a coating on the at least one calcium carbonate. At least one lignin is then located on the surface of at least one calcium carbonate.

According to a preferred embodiment of the invention, the at least one lignin is present in the composition in the form of a coating on the at least one calcium carbonate. Preferably, at least one lignin in the coating on the at least one calcium carbonate is a water-insoluble lignin, preferably kraft lignin.

A person skilled in the art knows how to prepare coated particles. Preferably, these coated particles are prepared by mixing the components of the composition of the invention in the presence of an organic solvent and then drying the mixture.

Mixing can be done sequentially or simultaneously in any order. For example, at least one lignin can be dissolved in an organic solvent and then at least one calcium carbonate can be added. Alternatively, at least one calcium carbonate can be dispersed in an organic solvent and then at least one lignin can be added. According to another embodiment, all compounds can be mixed at the same time.

Mixing can be carried out under normal mixing conditions. Those skilled in the art will adapt these mixing conditions (such as mixing pallet configuration and mixing speed) according to their process equipment. It is understood that any suitable method of mixing can be used.

In one embodiment, the mixing is carried out at a temperature in the range of 15-120°C, more preferably 20-110°C, most preferably 30-100°C. Mixing can be performed for at least 1 second, at least 10 seconds, at least 30 seconds, at least 1 minute, at least 10 minutes, or at least 1 hour.

Drying can be carried out in a single step, such as spray drying, or in at least two steps, for example applying a first heating step to the calcium carbonate, thereby reducing the associated moisture content. It can be implemented by The total residual moisture content can be further reduced by applying a second heating step to the calcium carbonate. When this drying is carried out by more than one drying step, the first step can be carried out by heating in a stream of hot air, while the second and further drying steps are preferably carried out by indirect heating. implement.

The obtained at least one calcium carbonate coated with at least one lignin may be further deagglomerated, for example during the grinding process. Generally, the comminution step can be carried out using any conventional comminution equipment, i.e. ball mills, rod mills, vibratory mills, e.g. under conditions such that purification occurs primarily as a result of impact by secondary objects. , roll crusher, centrifugal impact mill, vertical bead mill, attrition mill, pin mill, hammer mill, crusher, shredder, declamper, knife cutter, or other such equipment known to those skilled in the art. can be implemented.

According to one embodiment of the invention, the composition of the invention is in solid form, preferably in the form of particulate material. The term "particle" in the sense of this application refers to a material composed of a plurality of particles. The plurality of particles can be defined, for example, by their particle size distribution. The expression "particulate material" can include powders, particles, tablets, flakes or crumbles.

According to another embodiment of the invention, the composition of the invention is in the form of a slurry. A "suspension" or "slurry" in the sense of the present invention comprises undissolved solids, a solvent as defined above and any further additives and usually contains a large amount of solids, thus It may be more viscous and denser than the liquid from which it is formed.

For example, the amount of at least one calcium carbonate and at least one lignin is 0.1 to 20 wt%, preferably 0.2 to 15 wt%, more preferably 0.5 to 20 wt%, based on the total weight of the slurry. 10% by weight, most preferably 1-5% by weight.

According to a preferred embodiment of the present invention, the dry formulation comprises at least one calcium carbonate, preferably ground calcium carbonate, and 10% by weight, based on the dry weight of the at least one calcium carbonate, of at least one lignin, preferably alkaline Contains lignin. Preferably the lignin is present as a coating on at least one calcium carbonate. According to another preferred embodiment, the dry composition further comprises an organic solvent, preferably γ-valerolactone, in an amount of 30% by weight based on the dry weight of at least one calcium carbonate and It contains an organic solvent in an amount of 300% by weight. According to a preferred embodiment of the present invention, the dry formulation comprises ground calcium carbonate and 10% by weight based on the dry weight of at least one calcium carbonate alkaline lignin and 30% by weight based on the dry weight of at least one calcium carbonate. and preferably consisting of γ-valerolactone in an amount of 300% by weight based on the dry weight of lignin.

Fluid Compositions Fluid chemical and physical sunscreen compositions of the present invention comprise water and 1 to 100% by weight, based on the weight of water, of a dry composition according to the present invention.

The dry composition has already been described in detail above.

The water of the present invention can be selected from drinking water, process water, demineralized water, distilled water, rain water, reclaimed water, river water, and mixtures thereof. According to a preferred embodiment of the invention the water present in the fluid composition is potable water.

Drinking water, also known as potable water, is water that is safe for drinking or for use in food preparations. Rainwater/river water is obtained from rainwater/rivers. Reclaimed water is water that has been recycled and can be used in agriculture. Process water is water that is considered non-potable and is primarily used in connection with industrial plants, industrial processes and manufacturing facilities. Demineralized water is specially purified water that has had most or all of its mineral and salt ions removed, such as calcium ions, magnesium ions, sodium ions, chloride ions, sulfate ions, nitrate ions, bicarbonate ions, etc. . Demineralized water is also known as deionized water. Distilled water is water that has been boiled to vapor and condensed back to liquid in a separate vessel.

According to one embodiment of the present invention, the fluid composition comprises water and, based on the weight of water, 1-99.8% by weight, preferably 5-95% by weight, even more preferably 10-90% by weight, Most preferably it contains 15-85% by weight of the dry composition according to the invention.

According to one embodiment of the invention, the fluid composition further comprises a surfactant. A "surfactant" in the sense of the invention is a substance that reduces the surface tension (or interfacial tension) between two different compounds.

Any surfactant suitable for use in combination with calcium carbonate and/or lignin can be present in the compositions of the present invention. Such surfactants are known to those skilled in the art and are commercially available.

According to a preferred embodiment of the invention, the surfactant is acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, isocrotonic acid, aconitic acid (cis or trans), mesaconic acid, sinapinic acid , undecylenic acid, angelic acid, canelic acid, hydroxyacrylic acid, acrolein, acrylamide, acrylonitrile, dimethylaminoethyl methacrylate, vinylpyrrolidone, vinylcaprolactam, ethylene, propylene, isobutylene, diisobutylene, vinyl acetate, styrene, α-methylstyrene, selected from the group consisting of methyl vinyl ketone, esters of acrylic and methacrylic acid, organomodified trisiloxanes, PEG, polyglycerol-esters, sophorolipids, polyether monomers and/or comonomers, and mixtures thereof, most preferably Poly(acrylic acid) and/or poly(methacrylic acid).

Additionally or alternatively, a surfactant in an amount of 0.0001 to 0.2% by weight, based on the dry weight of the at least one calcium carbonate of (a) and the at least one lignin of (b) is present in the fluid composition, preferably in an amount of 0.001 to 0.1 weight percent, and most preferably in an amount of 0.005 to 0.05 weight percent.

According to a preferred embodiment of the invention, the composition comprises a surfactant, preferably acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, isocrotonic acid, aconitic acid (cis or trans), mesaconic acid, sinapinic acid, undecylenic acid, angelic acid, canelic acid, hydroxyacrylic acid, acrolein, acrylamide, acrylonitrile, dimethylaminoethyl methacrylate, vinylpyrrolidone, vinylcaprolactam, ethylene, propylene, isobutylene, diisobutylene, vinyl acetate , styrene, α-methylstyrene, methyl vinyl ketone, esters of acrylic and methacrylic acid, organomodified trisiloxanes, PEG, polyglycerol-esters, sophorolipids, polyether monomers and/or comonomers, and mixtures thereof a surfactant selected from the group, most preferably poly(acrylic acid) and/or poly(methacrylic acid), or the surfactant comprises at least one calcium carbonate of (a) and (b) in an amount of 0.0001-0.2% by weight, preferably in an amount of 0.001-0.1% by weight, most preferably 0.005-0.05% by weight, based on the dry weight of at least one lignin of % in the composition.

According to another preferred embodiment of the invention, the composition comprises a surfactant, preferably acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, isocrotonic acid, aconitic acid ( cis or trans), mesaconic acid, sinapinic acid, undecylenic acid, angelic acid, canelic acid, hydroxyacrylic acid, acrolein, acrylamide, acrylonitrile, dimethylaminoethyl methacrylate, vinylpyrrolidone, vinylcaprolactam, ethylene, propylene, isobutylene, diisobutylene, vinyl acetate, styrene, α-methylstyrene, methyl vinyl ketone, esters of acrylic and methacrylic acid, organomodified trisiloxanes, PEG, polyglycerol-esters, sophorolipids, polyether monomers and/or comonomers, and mixtures thereof and most preferably poly(acrylic acid) and/or poly(methacrylic acid), and the surfactant comprises at least one calcium carbonate of (a) and ( b) in an amount of 0.0001-0.2% by weight, preferably in an amount of 0.001-0.1% by weight, most preferably 0.005-0. 05% by weight in the composition.

Such surfactants are known to those skilled in the art and are commercially available. According to an exemplary embodiment, the surfactant is a polyether trisiloxane (Break-Thru S200), commercially available from Evonik Nutrition & Care GmbH.

According to a preferred embodiment of the invention, the fluid composition of the invention comprises, in addition to water, an organic solvent as defined above.

Preferably, the organic solvent is miscible with water in any ratio, preferably the ratio of water:organic solvent is from 100:0.1 to 100:200, based on the weight of water and the dry weight of the organic solvent. , preferably 100:1 to 100:150, more preferably 100:5 to 100:120, most preferably 100:10 to 100:100.

According to one embodiment of the invention, the fluid composition consists solely of calcium carbonate, lignin and water. According to another preferred embodiment of the invention, the fluid composition consists solely of calcium carbonate, lignin, organic solvent and water. According to another preferred embodiment of the invention, the fluid composition consists solely of calcium carbonate, lignin, organic solvents, surfactants and water.

According to one embodiment of the present invention, water is present in an amount of 0.1 to 50% by weight, based on the dry weight of the at least one calcium carbonate of (a) and the dry weight of the at least one lignin of (b) It is present in the fluid composition, more preferably in an amount of 0.5-40% by weight, most preferably in an amount of 1-35% by weight.

Those skilled in the art know how to prepare such fluid compositions. Preferably, these fluid compositions are prepared by mixing water with the dry composition according to the invention. Alternatively, these fluid compositions are prepared by mixing water with the ingredients of the dry compositions according to the present invention.

Mixing can be done sequentially or simultaneously in any order. For example, the dry composition can be added to water in one or several portions. Alternatively, at least one calcium carbonate, at least one lignin, and optional organic solvent can be added to water in any order. According to another embodiment, all these compounds can be mixed at the same time.

Mixing can be carried out under normal mixing conditions. Those skilled in the art will adapt these mixing conditions (such as mixing pallet configuration and mixing speed) according to their process equipment. It is understood that any suitable method of mixing can be used.

In one embodiment, the mixing is carried out at a temperature in the range of 15-100°C, more preferably 20-95°C, most preferably 30-90°C. Mixing can be performed for at least 1 second, at least 10 seconds, at least 30 seconds, at least 1 minute, at least 10 minutes, or at least 1 hour.

The fluid composition of the present invention is in the form of a slurry. A "suspension" or "slurry" in the sense of the present invention comprises undissolved solids, a solvent as defined above and any further additives and usually contains a large amount of solids, thus It may be more viscous and denser than the liquid from which it is formed.

For example, the amount of at least one calcium carbonate and at least one lignin is 0.1 to 20 wt%, preferably 0.2 to 15 wt%, more preferably 0.5 to 20 wt%, based on the total weight of the slurry. 10% by weight, most preferably 1-5% by weight.

According to a preferred embodiment, the fluid composition comprises about 5% by weight of the dry composition, based on the weight of water, and, based on the dry weight of (a) at least one calcium carbonate and (b) at least one lignin, about 0.05% by weight of surfactant. According to a preferred embodiment of the present invention, the fluid composition comprises about 5% by weight of the dry composition, based on the weight of water, and (a) at least one calcium carbonate and (b) at least one dried lignin. and preferably consisting of about 0.05% by weight of a surfactant, wherein the dry composition comprises ground calcium carbonate and 10% by weight, based on the dry weight of the at least one calcium carbonate. % alkaline lignin and γ-valerolactone in an amount of 30% by weight based on the dry weight of the at least one calcium carbonate and 300% by weight based on the dry weight of the lignin, preferably from these Become. Preferably, the surfactant is polyethertrisiloxane.

Emulsions The chemical and physical sunscreen emulsions of the present invention comprise water-in-oil or oil-in-water mixtures, based on the weight of the water-in-oil or oil-in-water mixtures, from 0.1 to 100% by weight. of the dry composition according to the present invention.

The dry composition has already been described in detail above. Furthermore, water has already been discussed above.

An emulsion in the sense of the present invention is a mixture of two or more liquids, which liquids are usually immiscible, and one liquid (the dispersed phase) is dispersed in the other (the continuous phase). . An oil-in-water emulsion according to the present invention is an emulsion in which oil is the dispersed phase and water is the continuous phase. A water-in-oil emulsion according to the present invention is an emulsion in which water is the dispersed phase and oil is the continuous phase.

Oils in the sense of the invention are liquid or solid silicone and/or hydrocarbon-containing compounds. The oil of the invention can be any oil suitable for the compositions of the invention. A person skilled in the art knows how to choose such oils. Oils are known to those skilled in the art and are commercially available.

Any oil known to those skilled in the art as suitable for cosmetic formulations can be used. For example, the oil can be selected from the group comprising alkane coconut esters, polydimethylsiloxanes, polyalkylmethylsiloxanes, silicones, petroleum jelly such as petrolatum, vegetable oils such as palm oil, esters of vegetable oils, and mixtures thereof. Preferably, the at least one oil is alkane coconut ester or petrolatum.

Preferably, the emulsions according to the invention contain water and oil in a ratio of 100:0.1 to 100:1000, preferably 100:1 to 100:700, more preferably 100:2, based on the weight of water and dry oil. 5 to 100:500, most preferably 100:10 to 100:300.

Emulsions according to the invention may contain further compounds such as dispersants, emulsifiers, preservatives, active agents, cosmetic ingredients, color pigments, skin-active substances.

According to one embodiment of the invention, the emulsion consists only of calcium carbonate, lignin and a water-in-oil or oil-in-water mixture. According to another preferred embodiment of the invention, the emulsion consists only of calcium carbonate, lignin, organic solvent and water-in-oil or oil-in-water mixtures. According to another preferred embodiment of the invention, the emulsion consists only of calcium carbonate, lignin, organic solvents, skin-active substances and water-in-oil or oil-in-water mixtures.

According to one embodiment of the present invention, the emulsion comprises a water-in-oil or oil-in-water mixture and from 0.1 to 15% by weight, preferably from 0.25 to 10% by weight, more preferably 0.5-5% by weight, most preferably 1-3% by weight of the dry composition according to the present invention.

Alternatively, the amount of at least one calcium carbonate and at least one lignin is 0.1-15% by weight, preferably 0.25-10% by weight, more preferably 0.5-5% by weight, based on the total weight of the emulsion. %, most preferably in an amount of 1-3% by weight.

A person skilled in the art knows how to prepare such emulsions. Preferably, these emulsions are prepared by first preparing a water-in-oil or oil-in-water mixture and then mixing the dry composition according to the invention with these emulsions. Alternatively, these emulsions are prepared by mixing all the ingredients and then emulsifying the mixture.

Mixing and emulsification can be done sequentially or simultaneously in any order. For example, the dry composition can be added in one or several portions to a water-in-oil or oil-in-water mixture. Alternatively, at least one calcium carbonate, at least one lignin, and optional organic solvent can be added in any order to the water-in-oil or oil-in-water mixture. According to another embodiment, all these compounds can be mixed at the same time. Alternatively, the dry composition can be mixed with water and oil in any order, or in one or several parts simultaneously, and then the mixture is emulsified.

Mixing and/or emulsification can be carried out under conventional mixing and/or emulsification conditions. A person skilled in the art will adapt these mixing and/or emulsifying conditions (such as mixing pallet configuration and mixing speed) according to his process equipment. It is understood that any suitable mixing and/or emulsifying method can be used.

In one embodiment, mixing and/or emulsification is performed at a temperature in the range of 15-100°C, more preferably 20-95°C, most preferably 30-90°C. Mixing and/or emulsification can be performed for at least 1 second, at least 10 seconds, at least 30 seconds, at least 1 minute, at least 10 minutes, or at least 1 hour.

According to a preferred embodiment of the invention, the emulsion is a water-in-oil emulsion and, based on the weight of the water-in-oil mixture, 0.25 to 10% by weight, preferably about 5% by weight of the dry composition according to the invention. Including things. Preferably, emulsions according to the invention comprise water and oil in a ratio of 100:10 to 100:300, preferably about 100:200, based on the weight of water and dry oil. Dry compositions according to the present invention preferably comprise about 10% by weight of at least one lignin, preferably alkaline lignin, based on the dry weight of the at least one calcium carbonate.

The inventors have surprisingly found that the compositions described above, ie dry and fluid compositions and emulsions, provide sufficient or improved chemical and physical sun protection. More precisely, the inventors have surprisingly found that the compositions of the invention are able to react by different mechanisms, namely by reflecting UV-B and/or UV-A radiation and by UV-B and/or UV-A radiation. It has been found that by absorbing UV-A radiation, it provides two different mechanisms for UV-B and/or UV-A protection for living cells, especially plants and plant parts, and human skin.

UV-B and/or UV-A protection can be measured by transmission and absorbance measurements. UV-visible spectroscopy or UV-visible spectrophotometry and near-infrared spectroscopy (UV-Vis or UV/Vis and NIR) means absorption spectroscopy in the UV-visible and near-infrared spectral region, or reflection spectroscopy Say. This means that the method uses light in the visible and adjacent regions. Absorption or reflection in this range directly affects the perceived color of the chemicals involved. In this region of the electromagnetic spectrum, atoms and molecules undergo electronic transitions. As used herein, transmittance and absorbance are measured by a double-beam PerkinElmer Lambda 950 UV/Vis/NIR spectrometer equipped with a 150 mm integrating sphere with PMT and InGaAs detectors.

According to one embodiment of the present invention, the composition/emulsion of the present invention is characterized by a reduction in living cells, e.g. plant and plant parts, especially fruits, and improved UV-B and/or UV-A protection for human skin.

"Identical composition/identical emulsion" in the sense of the present invention means that the composition does not contain both at least one calcium carbonate and at least one lignin, except that it contains only calcium carbonate or only lignin. refers to a composition/emulsion consisting of the same ingredients in the same amounts as the composition/emulsion of the present invention. Missing components are replaced with other components.

According to one preferred embodiment of the present invention, the composition/emulsion of the present invention has at least one composition/emulsion in the range of 280 nm to 320 nm or >320 nm compared to the same composition/emulsion comprising only at least one calcium carbonate. It has improved transmittance and absorbance in the range of -400 nm, most preferably in the range of 280 nm to 400 nm.

Furthermore, the inventors have surprisingly found that the compositions/emulsions of the invention can be produced easily and quickly, are inexpensive and, above all, easy to handle. More precisely, the compositions/emulsions of the invention can be readily prepared by mixing and/or emulsifying the components of the compositions/emulsions of the invention as described above.

Furthermore, when at least one lignin is present in this composition/emulsion in the form of a coating on at least one calcium carbonate, the inventors have found that these coated particles are formed by a different mechanism, i.e. , by reflecting UV-B and/or UV-A radiation and by absorbing UV-B and/or UV-A radiation, against living cells, in particular plants and plant parts, and human skin. have been found to provide two different mechanisms for UV-B and/or UV-A protection. Since calcium carbonate and lignin are non-toxic to humans and have no harmful effects on the environment, these coated particles are non-toxic to humans and have no harmful effects on the environment. don't give Furthermore, if at least one lignin in the coating on the at least one calcium carbonate is a water-insoluble lignin, such as kraft lignin, the inventors have surprisingly found that this coating is similar to the coated calcium carbonate particles. was found to adhere to calcium carbonate even after redispersion in water. Therefore, even if the particles are dispersed in water, the coating layer is maintained. For example, when such compositions are on plants and plant parts, the lignin cannot be easily washed away by rain or by irrigation water. When such a water-based composition is formulated into a cosmetic formulation, the lignin is attached to the surface of the calcium carbonate and is not easily washed off the human skin by perspiration.

Use of the Compositions and Emulsions The compositions of the invention and the emulsions of the invention are used for sun protection.

More precisely, the compositions according to the invention, comprising the dry composition according to the invention and the fluid composition according to the invention, are used for sun protection of plants and plant parts, wherein the sun protection is including physical and chemical protection.

This can be readily done by applying the compositions of the invention to the plants and plant parts by any suitable method known to those skilled in the art, such as spraying, painting or dipping. According to a preferred method, the plants and plant parts are sprayed with the compositions of the invention. Devices for spraying compositions are known to those skilled in the art and are commercially available.

According to one embodiment of the invention, plants and plant parts are fruits, vegetables, trees, seeds, leaves, wood, nuts, agricultural crops, crop plants and flowers, especially apples, oranges, citrons, cherries. , pears, plums, bananas, or mangoes.

As already indicated above, the inventors have surprisingly found that the compositions described above provide sufficient sun protection for plants and plant parts, especially fruits. In particular, the inventors have surprisingly found that (a) at least one calcium carbonate and (b) from 0.1% to 100% by weight based on the dry weight of the at least one calcium carbonate of (a) It has been found that using compositions comprising at least one lignin, the compositions provide improved sun protection, i.e., sun protection including physical and chemical protection for plants and plant parts. Furthermore, when the composition according to the invention is used for sun protection of plants and plant parts, another advantage is that due to the calcium carbonate in the composition, the composition provides the plant with additional calcium nutrients. to provide. Yet another advantage is that when the fluid composition is used on plants and plant parts, the layer of composition formed on the plants and plant parts also repels insects.

Furthermore, the invention relates to the use of the emulsion according to the invention. More precisely, the present invention relates to cosmetic products of emulsions comprising a water-in-oil or oil-in-water mixture and 1 to 100% by weight of the dry composition according to the invention, based on the weight of the water-in-oil or oil-in-water mixture. It relates to the use for chemical and physical sun protection in formulations.

This can be easily done by applying the emulsion of the invention to the cosmetic formulation by any suitable method known to those skilled in the art, for example by mixing, dispersing or emulsifying. According to a preferred method, the ingredients of the cosmetic formulation are mixed with the emulsion of the invention. Devices are therefore known to those skilled in the art and commercially available.

According to one embodiment of the invention, the cosmetic formulations are sunscreen products, facial makeup products, hair care products, hair styling products, nail care products, hand care products, skin care products and mixtures thereof.

According to another preferred embodiment, the at least one lignin is present in the cosmetic formulation in the form of a coating on the at least one calcium carbonate. Additionally or alternatively, at least one lignin in the cosmetic formulation is a water-insoluble lignin, preferably kraft lignin.

According to another preferred embodiment, the at least one lignin is present in the cosmetic formulation in the form of a coating on at least one calcium carbonate, and the at least one lignin in the cosmetic formulation is a water-insoluble lignin, preferably is kraft lignin.

According to another preferred embodiment, at least one lignin is present in the cosmetic formulation in the form of a coating on at least one calcium carbonate, or at least one lignin in the cosmetic formulation is a water-insoluble lignin, preferably is kraft lignin.

As already mentioned above, the inventors have surprisingly found that the compositions described above provide sufficient sun protection for living cells, especially human skin. The inventors have surprisingly used an emulsion containing a water-in-oil or oil-in-water mixture and 1 to 100% by weight of the dry composition according to the invention, based on the water-in-oil or oil-in-water mixture. It has now been found that this composition provides improved sun protection, ie sun protection that includes physical and chemical protection for human skin.

Furthermore, the present invention relates to cosmetic formulations comprising the emulsions of the invention as described above. More precisely, the present invention relates to a cosmetic product comprising an emulsion comprising a water-in-oil or oil-in-water mixture and 1 to 100% by weight of the dry composition according to the invention, based on the weight of the water-in-oil or oil-in-water mixture. Regarding formulations.

According to one embodiment, the at least one lignin is present in the cosmetic formulation in the form of a coating on at least one calcium carbonate and/or the at least one lignin is water-insoluble lignin, preferably kraft lignin.

According to another embodiment of the invention, the cosmetic formulation is a sunscreen product, a facial makeup product, a hair care product, a hair styling product, a nail care product, a hand care product, a skin care product, and mixtures thereof.

The scope and benefits of the present invention can be better understood based on the following examples, which are intended to illustrate certain embodiments of the invention and are non-limiting.

FIG. 1 is a schematic of a diffuse reflectance measurement using a sample placed at the reflecting port of an integrating sphere. FIG. 2 is a schematic diagram of an absorbance measurement using a sample placed in the center of an integrating sphere. FIG. 3 is a schematic of a transmittance measurement using a sample placed at the transmission port of an integrating sphere. FIG. 4 shows the Kubelka-Munk function of a dry composition comprising at least one ground calcium carbonate (GCC) coated with at least one lignin and a dry composition comprising ground calcium carbonate (GCC). Absorption derived from diffuse reflection used. FIG. 5 shows a fluid composition containing 0.1% by weight ground calcium carbonate (GCC) used as a reference and a fluid composition with 0.1% by weight ground calcium carbonate (GCC) coated with at least one lignin. It shows the absorbance of a substance. FIG. 6 shows coatings realized with a fluid composition comprising 5% by weight ground calcium carbonate (GCC) and a fluid composition comprising 5% by weight ground calcium carbonate (GCC) coated with at least one lignin. Transmission as a function of coating density at 300 nm, 360 nm and 550 nm is shown. FIG. 7 shows a water-in-oil emulsion containing only 5% by weight ground calcium carbonate (GCC) and a water-in-oil emulsion containing 5% by weight ground calcium carbonate (GCC) coated with at least one lignin. , 300 nm and 360 nm transmission.

1. Measurement method The measurement method carried out in the examples will be described below.

Reflectance, Absorbance and Transmittance Measurements Reflectance, absorbance and transmittance analyzes were performed using a double-beam PerkinElmer Lambda 950 UV/Vis/NIR spectrophotometer equipped with a 150 mm integrating sphere with PMT and InGaAs detectors. rice field.

The dry compositions were measured by diffuse reflectance spectroscopy, as shown in FIG. The analysis was performed with powder samples loaded into an aluminum cup positioned flush with the reflecting port of the integrating sphere. To obtain a proxy for the absorption spectrum of the dry composition, the measured diffuse reflectance spectrum was converted using the Kubelka-Munk equation: K/S=(1−R) ² /2R. converted by where R is the reflectance and K and S are the absorption and scattering coefficients, respectively. The spectrophotometer was scanned from 280 nm to 800 nm in steps of 2 nm. A Spectralon® white standard was used as a 100% baseline.

Fluid composition was determined by absorbance analysis. The fluid composition was diluted with deionized water to a final solids content of 0.1% by weight based on the total weight of the fluid composition. Diluted samples were injected into a 1 cm path length quartz cuvette and positioned using a holder centrally mounted inside the integrating sphere as shown in FIG. This arrangement allows both the transmittance (T) and reflectance (R) of the sample to be measured simultaneously, thus leading to absorbance (A) as A=−log(T+R) in one single measurement. be able to. This technique is also known as transflectance analysis. A 0.1 wt% suspension of ground calcium carbonate (GCC) in deionized water was used as a reference. The spectrophotometer was scanned from 280 nm to 800 nm in steps of 2 nm. Each sample was prepared and measured in triplicate, and the average absorption spectrum was calculated.

The fluid composition was also analyzed using the transmittance technique. The fluid composition was applied onto a quartz plate (50 x 50 x 3 mm) using an airbrush. The coated plates were dried in an oven at 50°C. Coating densities ranging from 0.4 g/m ² to 16.4 g/m ² were achieved by spraying appropriate amounts of the fluid composition. The sample thus obtained was placed at the entrance of an integrating sphere, as shown in FIG. Transmission measurements were made in the range 280 nm to 700 nm in steps of 2 nm. Four replicates were performed for each sample at different sample positions obtained by rotating the coated plate 90° about the axis of the incident beam. An average transmittance spectrum of the sample was then calculated. Finally, the average transmittance spectra of the samples were normalized to the average transmittance of the bare quartz plate.

Emulsions were analyzed using the transmittance technique. Samples were prepared by applying 30 mg of emulsion onto a roughened PMMA plate (HD6 Helioplate from Helioscreen). The coated plates were dried in the dark for 30 minutes at room temperature. The sample thus obtained was placed at the entrance of an integrating sphere, as shown in FIG. Transmission measurements were made in the range 280 nm to 700 nm in steps of 2 nm. Four replicate samples were prepared and four replicates were performed for each sample at different sample positions obtained by rotating the coated plate 90° about the axis of the incident beam. An average transmittance spectrum of the sample was then calculated. Finally, the average transmittance spectra of the samples were normalized to the average transmittance of the bare PMMA plate.

Particle Size Distribution Weight-based median particle size d ₅₀ (wt) was determined by the sedimentation method, an analysis of sedimentation behavior in a gravitational field. This measurement was performed using a Sedigraph® 5100 from Micromeritics Instrument Corporation, USA. This method and instrumentation are known to those skilled in the art and are commonly used to determine the particle size distribution of fillers and pigments. This measurement was carried out in an aqueous solution of 0.1% by weight Na ₄ P ₂ O ₇ . The samples were dispersed using a high speed stirrer and sonication.

BET specific surface area (SSA) of material
BET specific surface area was measured via BET treatment according to ISO 9277:2010 using nitrogen following conditioning of the samples by heating at 250° C. for 30 minutes. Prior to such measurements, the samples were filtered, rinsed and dried in an oven at 110°C for at least 12 hours.

Materials Used in the Examples and Preparation of Samples Calcium Carbonate: Marble-type ground natural calcium carbonate (GCC) with a calcium carbonate content greater than 97.5% by weight. This ground calcium carbonate has a weight median particle size d ₅₀ value of 0.95 μm and a BET specific surface area of 5.7 m ² /g measured by the BET nitrogen method.
Lignin: Alkaline lignin, commercially available from Sigma-Aldrich under number 370959-100G Organic solvent: γ-valerolactone (GVL), commercially available from Sigma-Aldrich under number V403-100G
Water: Distilled water Oil-in-water mixture: Unguentum Alcoholum Lanae aquosum available from Caelo under item number 3074, batch number 181705
Surfactant: Polyether trisiloxane commercially available from Evonik under the name Break-thru S200

The following dry compositions were prepared:
20 g of GCC was dried at 100° C. overnight. 2g of at least one lignin was solubilized in 6g of organic solvent. Both components were maintained with mixing at ambient temperature using a standard magnetic stir bar until complete solubilization of the alkaline lignin. The lignin solution was added dropwise to the GCC while manually mixing the GCC for a homogeneous coating. The lignin-coated GCC was dried overnight at 100°C. If necessary, the GCCs are manually disaggregated using a standard laboratory mortar.

The following fluid compositions were prepared:
Water is mixed with the above dry composition, the composition comprising 5% by weight of the above dry composition based on the total weight of the slurry and 0.05% by weight of the surfactant based on the total weight of the slurry. included.

The following emulsions were prepared:
For this composition a commercially available water-in-oil mixture was used. The above dry composition is added to the water-in-oil mixture with stirring in an amount of 5% by weight based on the weight of the water-in-oil mixture.

Diffuse reflectance test 01
The diffuse reflectance of the dry composition prepared above was measured and converted to an absorption spectrum using the Kubelka-Munk function. As can be seen from FIG. 4, the dry composition containing lignin-coated GCC (filled circles) clearly shows significantly greater UV absorption compared to the dry composition containing only GCC (open circles, see). From FIG. 4 it can be concluded that the lignin coating applied on the GCC provides improved UV absorption in the claimed range.

Absorbance test 01
The absorbance of the fluid composition prepared above is measured. As can be seen from FIG. 5, fluid compositions containing lignin-coated GCC (filled circles) clearly show significantly greater UV absorption compared to fluid compositions containing only GCC (open circles, see). From FIG. 5 it can be concluded that the lignin coating applied on the GCC provides improved UV absorption in the claimed range.

Transmittance test 01
FIG. 6 shows the average transmittance curves as a function of coating density for lignin-coated GCC and standard GCC used in the fluid compositions prepared above. Reported transmittance values are evaluated at wavelengths of 300 nm (UVB), 360 nm (UVA), and 550 nm (Vis). As an example, at a coating density of about 5 g/m ² , the transmittance of lignin-coated GCC is about 36% (UVB ) and 29% (UVA) lower. This same effect is much less pronounced or not observed in the Vis region. This is because in the Vis region, light is primarily attenuated by reflection mechanisms from GCC particles in this wavelength range. Therefore, the combination of at least one lignin and at least one calcium carbonate provides better UV cause attenuation.

Transmittance test 02
Figure 7 is a water-in-oil emulsion containing 5 wt% lignin-coated GCC (hatched bars) and 5 wt% standard GCC, evaluated at 300 nm (UVB) and 360 nm (UVA). Average transmittance of water-in-oil emulsions (open bars) is shown. Permeability values are clearly lower for lignin-coated GCC compared to standard GCC. From Figure 7 it can be concluded that cosmetic emulsions containing dry formulations according to the invention provide improved UV absorption.

Claims (17)

Chemical and physical sunscreen dry compositions containing:
(a) at least one calcium carbonate; and (b) from 0.1% to 100% by weight of at least one lignin, based on the dry weight of the at least one calcium carbonate of (a). said calcium carbonate consists of ground calcium carbonate (GCC), preferably marble, limestone and/or chalk; precipitated calcium carbonate (PCC), preferably vaterite, calcite and/or aragonite; and mixtures thereof. A composition according to claim 1, selected from the group, most preferably said calcium carbonate is ground calcium carbonate. 3. The composition of claim 1 or 2, wherein said at least one calcium carbonate comprises:
(a) weight median particle size _d50 value of 0.05 μm to 20 μm, preferably 0.25 μm to 10 μm, most preferably 0.5 μm to 8 μm, and/or (b) ≦100 μm, preferably ≦60 μm, more preferably is ≦45 μm, most preferably ≦20 μm, and/or (c) 0.5-100 m ² /g, preferably 0.5-50 m ² /g, measured by _the BET nitrogen method, More preferably 0.5 to 35 m ² /g, most preferably 0.5 to 10 m ² /g specific surface area (BET). water-soluble or wherein said at least one lignin is selected from the group consisting of natural lignin, Clarson lignin, hydrolyzed lignin, ground lignin, soda lignin, organosolv lignin, kraft lignin, sulfonated lignin, and mixtures thereof; water-insoluble lignin,
Preferably, said at least one lignin is a water-insoluble lignin selected from the group consisting of Clason lignin, Kraft lignin, and mixtures thereof;
Most preferably, said at least one lignin is kraft lignin.
A composition according to any one of claims 1-3. said at least one lignin, based on the dry weight of said at least one calcium carbonate of (a), in an amount of 1-50% by weight, preferably in an amount of 3-30% by weight, most preferably 5-25% by weight; A composition according to any one of claims 1 to 4, present in said composition in an amount of %. the composition further comprising an organic solvent;
preferably in an amount of 5-50% by weight, more preferably in an amount of 10-40% by weight, most preferably in an amount of 15-35% by weight, based on the dry weight of said at least one calcium carbonate of (a) and/or preferably in an amount of 100 to 500% by weight, more preferably in an amount of 150 to 450% by weight, most preferably 200 to 300 in the amount of % by weight,
A composition according to any preceding claim, comprising an organic solvent. The organic solvent is selected from the group consisting of hexane, toluene, methanol, ethanol, dioxane, acetone, dimethylsulfoxide, dimethylformamide, ethylene glycol, ethyl acetate, glycerol, γ-valerolactone, polyethylene glycol, polypropylene glycol, and mixtures thereof. selected,
more preferably selected from the group consisting of ethylene glycol, ethyl acetate, glycerol, γ-valerolactone, polyethylene glycol, polypropylene glycol, and mixtures thereof;
Most preferably, it is γ-valerolactone,
7. A composition according to claim 6. Said at least one lignin is present in said composition in the form of a mixture with said at least one calcium carbonate or in the form of a coating on said at least one calcium carbonate, preferably said at least one A composition according to any one of the preceding claims, present as a coating on one piece of calcium carbonate. 9. A composition according to claim 8, wherein said at least one lignin in said coating on said at least one calcium carbonate is a water-insoluble lignin, preferably kraft lignin. A fluid chemical and physical sunscreen composition comprising water and 1-100% by weight, based on the weight of said water, of a dry composition according to any one of claims 1-9. the composition further comprising a surfactant;
Preferably, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, isocrotonic acid, aconitic acid (cis or trans), mesaconic acid, sinapinic acid, undecylenic acid, angelic acid, canelic acid, hydroxy acrylic acids, acrolein, acrylamide, acrylonitrile, dimethylaminoethyl methacrylate, vinylpyrrolidone, vinylcaprolactam, ethylene, propylene, isobutylene, diisobutylene, vinyl acetate, styrene, α-methylstyrene, methyl vinyl ketone, esters of acrylic and methacrylic acid, selected from the group consisting of organomodified trisiloxanes, PEG, polyglycerol-esters, sophorolipids, polyether monomers and/or comonomers, and mixtures thereof, most preferably poly(acrylic acid) and/or poly(methacrylic acid), and/or wherein said surfactant is between 0.0001 and 0, based on the dry weight of said at least one calcium carbonate of (a) and said at least one lignin of (b) present in said composition in an amount of .2% by weight, preferably in an amount of 0.001-0.1% by weight, most preferably in an amount of 0.005-0.05% by weight;
11. The composition of claim 10. a water-in-oil or oil-in-water mixture and 0.1 to 100% by weight, based on the weight of said water-in-oil or oil-in-water mixture, of a dry composition according to any one of claims 1 to 9, Emulsions for chemical and physical sun protection. Use of a composition according to any one of claims 1 to 11 for sun protection of plants and plant parts, wherein said sun protection comprises chemical and physical protection. 14. Use according to claim 13, wherein the plants and plant parts are fruits, vegetables, trees, seeds, leaves, wood, nuts, agricultural crops, crop plants and flowers. Use of the emulsion according to claim 12 for chemical and physical sun protection in cosmetic formulations. 16. Use according to claim 15, wherein said at least one lignin is present in the form of a coating on said at least one calcium carbonate and/or said at least one lignin is a water-insoluble lignin, preferably kraft lignin. 16. Use according to claim 15, wherein the cosmetic formulation is a sunscreen product, a facial makeup product, a hair care product, a hair styling product, a nail care product, a hand care product, a skin care product, and mixtures thereof.

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